Back titration with mercuric nitrate in alkaline medium analysis of tertiary mixtures of mercury(II) with some other metals

Summary Tertiary mixtures each containing mercury(II) were analysed by simple procedures involving combination between the recent method of back titration with mercuric nitrate in alkaline medium, and the volumetric methods which make use of masking agents as cyanide. The content of mercury(II) in most mixtures is determined potentiometrically with potassium iodide using the silver amalgam as indicator electrode. End points are attended with fair accuracy within 0.02 ml titrant and with reasonable jumps from 60 to 90 mv per 0.1 ml of mercuric nitrate solution or from 170 to 200 mv per 0.1 ml of potassium iodide solution.     

Titration of 6-aminopenicillanic acid with mercury (II) solution.

A simple, absolute method for the determination of 6-aminopenicillanic acid (6-APA) is described. The method involves two titrations with mercury(II) nitrate solution at pH 4.8, the first on an untreated solution and the second on a solution which has been acetylated, alkali-hydrolysed, and neutralized. The first titration accounts for the degradation products of 6-APA; the second titration gives the sum of these products and the intact 6-APA in the sample. The method is rapid and accurate.     

Mercury-assisted solvolyses of alkyl halides : Simple procedures for the preparation of nitrate esters,acetate esters,alcohols and ethers

The reactions of a wide variety of alkyl halides with mercury(I) and/or (II) nitrate in 1,2-dimethoxyethane, mercury(II) acetate in acetic acid, aqueous mercury(II) perchlorate, and mercury(II) perchlorate in alcohol solvents have been investigated; as a result, simple high yield procedures for the conversion of alkyl halides into the corresponding nitrate esters, acetate esters, alcohols and ethers have been developed.     

Catalytic amperometric and catalytic constant-current potentiometric titrations of silver(I), palladium(II) and mercury(II)

Amperometry and constant-current potentiometry were used to follow the course of catalytic titrations of silver(I), palladium(II), and mercury(II) with potassium iodide. The Ce(IV)As(III) and Ce(IV)Sb(III) systems in the presence of sulphuric acid were used as indicator reactions. The possibilities of application of platinum, palladium, gold, graphite, and glassy-carbon indicator electrodes were investigated. Graphite appeared to be somewhat more advantageous than the other electrode materials. The effect of concentration of the components of the indicator reactions, the presence of organic solvents and acids on the shape of the catalytic titration curves was studied. Amounts of 30-3000 mug of silver(I) nitrate, 90-900 mug of palladium(II) chloride, 130-1300 mug of mercury(II) chloride, and 150-1500 mug of mercury(II) nitrate were determined with a relative standard deviation less than 1.0%. The results obtained were in good agreement with those of comparable methods. The catalytic titration method developed was applied to determination of mercury in Unguentum Hydrargyri.     

Potentiometric titration of trace amounts of mercury after a preliminary separation by a reduction method

Isolation and concentration of mercury by reduction of mercury(II) with acidic tin(II) chloride solution and absorption of mercury vapour in acidic permanganate solution is combined with potentiometric titration with dithiooxamide. The simple procedure is applicable to 5–100 ppb mercury in 1-dm³ samples. Recoveries from organomercurials are discussed.     

Determination of micromolar concentrations of iodide by electrothermal atomic absorption spectrometry

When a solution (at pH 3.4–4.8) containing iodide and mercury(II) nitrate in a graphite tube is heated by increasing the temperature at a uniform rate, two mercury absorption peaks appear because the decomposition temperature of mercury(II) iodide is higher than that of mercury(II) nitrate. Measurement of the second peak allows 1 × 10^-6–5 × 10^-5 M iodide to be determined with good reproducibility. Equimolar concentrations of cyanide, sulfide and thiosulfate interfered, but these anions could be destroyed with hydrogen peroxide. Interfering cations were removed by extraction of 8-quinolinol complexes.     

Mercurimetric Potentiometric Determination of Barbiturates Using a Solid-State Iodide Ion-Selective Electrode

Abstract

A simple potentiometric method is described for mercurimetric titration of barbiturates using a solid-state iodide ion-selective electrode. The optimum titration conditions involve the use of a borate buffer of pH 9–10 as a medium and mercury(II) perchlorate of pH 1.7–1.9 as a titrant. Under these conditions, titration curves with two sharp consecutive inflection breaks are obtained. The first inflection corresponds to quantitative and stoichiometric reaction of barbiturates with mercury(II) and the second break is due to the reaction of the buffer with the titrant. No interferences are caused by Cl^?, Br^?, PO₄ ^3- and many excipients and diluents commonly used in the drug formulations. Determination of barbiturates in various pharmaceutical preparations gives reproducible results with an average recovery of 99.1% of the nominal (st.dev. 0.3 %) and the method offers significant advantages over the titrimetric method of the British Pharmacopoeia.     

Behavior of mercury(II) salts in electrothermal atomic absorption spectrometry : Application to the Determination of Thiosulfate

Mercury(II) salts have different decomposition temperatures in a graphite tube or tantalum coil used for electrothermal atomic absorption spectrometry. The nitrate, perchlorate and acetate were spontaneously reduced to mercury vapor at room temperature, but the thiosulfate, sulfide, cyanide and bromide were reduced only on heating. Chloride and thiocyanate in a graphite furnace and iodide in a tantalum coil did not give mercury absorbance on heating. Thiosulfate (1–10 × 10^?6 M) was determined by addition to mercury(II) nitrate in acetate buffer, removing the response from the excess mercury(II) nitrate by drying below 100° C in the graphite furnace, and measuring the mercury absorbance on heating, which was proportional to the thiosulfate concentration.     

Determination of phosphite,hypophosphite, tellurium and mercury

A new catalytic oxidation procedure, involving the use of a cerium(IV) sulfate reagent in perchloric acid with a mixed silver(I)—manganese(II) perchlorate catalyst, has been developed for the determination of phosphite, hypophosphite, and tellurium. By this method 15—100 mg of phosphite, 5—35 mg of hypophosphite, and 10—105 mg of tellurium may be determined with standard deviations of ±0.17, ±0.32, and ±0.21% respectively. A direct titration procedure for mercury(I) is described using a ceric perchlorate solution as titrant with the mixed catalyst system. Samples from 65–510 mg may be analyzed with a standard deviation of ±0.36%.     

High frequency titrations: The mercury(ii)-thiocyanate reaction

Soluble complex-formation of mercury(II) thiocyanate has been studied oscillometrically. The titration of mercury(II) nitrate with thiocyanate gives one inflection corresponding to the formation of Hg(SCN)₂, while in the reverse titration the formation of Hg(SCN)⁺ is also indecated. The method is useful for a rapid determination of very small quantities of mercury or thiocyanate in highly dilute solutions. The titrations can be effected in presence of nitric acid provided its total acidity in the system does not exceed about $\text{1}\text{300}$N. Further Work on the mercury(II) -halide and mercury(II)-cyanide reactions is in progress.     

Novel mercury(II) complexes of porphyrins

Treatment of octa-alkylporphyrins (e.g. 1–3) with mercury(II) acetate in methylene chloride and tetrahydrofuran affords novel complexes (4) containing two porphyrin rings layered between three Hg atoms. A new type of stereoisomerism in regularly substituted porphyrins (e.g. 1a, 2a) is identified; it is observed by NMR spectroscopy and occurs because two forms of the complex (4) are possible, depending upon which faces of the porphyrin molecule are turned in towards the central Hg atom. The NMR spectra also indicate that in concentrated solution the double sandwich complexes (4) are stable towards disproportionation and recombination. On the basis of the inherent geometrical arrangements in the complex (4), an efficient NMR method for unambiguous identification of the four primary type isomers of the aetio- and copro-porphyrin series is described.

In very dilute solution, or in mixtures containing nucleophilic solvents such as pyridine, methanol, dioxan, or tetrahydrofuran (in the absence of excess mercury(II) acetate), the double sandwich complexes (4) are destroyed to afford normal 1:1 metalloporphyrins.     

Copper(II) complexes of 2-(pyrrolidinomethyl)- and 2-(3-pyrrolinomethyl)pyridine N-oxides

Summary This title pyridine N-oxides have been prepared and their copper(II) complexes isolated as perchlorate, tetrafluoroborate and nitrate salts. The ligands coordinatevia both the pyridine N-oxide oxygen and the amine nitrogen to give bis(ligand) complexes for the perchlorate and tetrafluoroborate salts. The nitrate solids have [CuL(NO₃)₂] stoichiometry with monodentate nitrato-ligands. The spectral properties of these complexes are compared to those of N-alkyl-and N,N-dialkyl2-picolinamine N-oxides as well as other 2-substituted pyridine N-oxides.NATO Fellow on leave from Istanbul Medical Faculty, Istanbul University.     

Rational approach to endo/exocoordinated heteronuclear macrocyclic network: supramolecular Hg(ll), Cu(ll), and Hg(ll)/Cu(ll) complexes of a NS4 macrocycle

A rationally designed sulfur-rich macrocycle L incorporating one pyridine and one benzo subunit was synthesized and structurally characterized. From the assembly reactions of L with copper(II) nitrate and mercury(II) iodide, an endocyclic monocopper(II) complex and an exocyclic dimercury(II) complex were prepared, respectively. On the basis of these results, the construction of a Hg(II)/Cu(II) heteronuclear 1D network complex with an endo/exocyclic coordination mode was achieved by one-pot assembly reaction of L with mercury(II) iodide in the presence of copper(II) nitrate.     

Adsorption of mercury(II) on macroreticular styrene-divinylbenzene copolymer beads

The adsorption characteristics of mercury(II) on several kinds of styrene-divinylbenzene copolymer beads having different surface properties were studied. It was found that the polymer beads selectively adsorbed mercury(II) from solutions over a wide range of pH with high efficiency. The amount of mercury(II) adsorbed increased with increase in specific surface area of the polymer beads and the adsorption behaviour was found to be of the Langmuir type. The presence of chloride strongly reduced the adsorption, but this interference was not observed with nitrate, sulphate, perchlorate, cadmium(II), cobalt(II), copper(II), nickel(II), silver(I) and zinc(II). More than 95% of the mercury(II) adsorbed on a column of polymer beads could be recovered with dilute hydrochloric acid.     

An electsochemical study of copper(II) nitrate and perchlorate in n,n-dimethylformamide

Polarographic, cyclic voltammetric and controlled-potential coulometric studies of copper(II) nitrate and perchlorate in dimethylformamide are reported. Copper(II) in copper(II) perchlorate solutions is directly reduced in a 2e step to copper metal at platinum electrodes and to a copper amalgam at mercury electrodes. Copper(II) in the presence of nitrate forms a complex of composition Cu(N0₃)₂ in DMF; the dissociation constant, measured polarographically, is 9 × lO^-5. The copper(II) nitrate complex is electrochemically reduced in two steps consisting of a reversible dissociation of the complex followed by direct reduction of copper(II) ion to copper(0). The diffusion coefficients of copper(II) ion and the copper(II) nitrate complex are 4.91 × lO^-6 cm² s^-1 and 4.33 × 10^-6 cm² s^-1, respectively.     

Coulometric titration of penicillins and penicillamine with mercury(II)

An absolute coulometric method based on the titration of hydrolysed penicillins with coulometrically generated mercury(II) is presented. An amalgamated gold plate is used as anode and the titration is performed in a pH 4.6 acetate buffer solution. The method gives values which deviate by less than 1% from values obtained by other absolute methods. The relative standard deviation for determination of penicillin G is 0.4%. The determinations of penicillamine and mixtures of penicillamine and penicilloate are also reported.     

An EXAFS spectroscopic, large-angle X-ray scattering, and crystallographic study of hexahydrated, dimethyl sulfoxide and pyridine 1-oxide hexasolvated mercury(II) ions

The structure of the solvated mercury(II) ion in water and dimethyl sulfoxide has been studied by means of large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) techniques. The distribution of the Hg-O distances is unusually wide and asymmetric in both solvents. In aqueous solution, hexahydrated [Hg(OH(2))(6)](2+) ions in a distorted octahedral configuration, with the centroid of the Hg-O distance at 2.38(1) A, are surrounded by a diffuse second hydration sphere with HgO(II) distances of 4.20(2) A. In dimethyl sulfoxide, the six Hg-O and HgS distances of the hexasolvated [Hg{OS(CH(3))(2)}(6)](2+) complex are centered around 2.38(1) and 3.45(2) A, respectively. The crystal structure of hexakis(pyridine 1-oxide)mercury(II) perchlorate has been redetermined. The space group R(-)3 implies six equal Hg-O distances of 2.3416(7) A for the [Hg(ONC(5)H(5))(6)](2+) complex at 100 K. However, EXAFS studies of this compound, and of the solids hexaaquamercury(II) perchlorate and hexakis(dimethyl sulfoxide)mercury(II) trifluoromethanesulfonate, also with six equidistant Hg-O bonds according to crystallographic results, reveal in all cases strongly asymmetric Hg-O distance distributions. Vibronic coupling of valence states in a so-called pseudo-Jahn-Teller effect probably induces the distorted configurations.     

Coulometric generation of hydrogen ions by oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone

Mercury(II)-chloride reacts with anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone in a precise stoichiometry ratio (1:2), and weakly ionized compounds of mercury with ketones are formed and equivalent quantity of HCl is released. The application of a mercury anode for the quantitative generation of H⁺ ions in 0.25 M sodium perchlorate in anhydrous methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone has been investigated. Current/potentials curves for the solvents, titrated bases, indicator and mercury showed that in these solvents mercury is oxidized at potentials much more negative than those for the titrated bases and other components present in the solution. The protons generated in this way have been used for the titration of some organic bases, with either visual or potentiometric end-point detection. The oxidation of mercury in methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone and the reaction of mercury ions with these solvents have been found to proceed with 100% current efficiency.     

Characterization of perchlorate in a new frozen human urine standard reference material

Perchlorate, an inorganic anion, has recently been recognized as an environmental contaminant by the US Environmental Protection Agency. Urine is the preferred matrix for assessment of human exposure to perchlorate. Although the measurement technique for perchlorate in urine was developed in 2005, the calibration and quality assurance aspects of the metrology infrastructure for perchlorate are still lacking in that there is no certified reference material (CRM) traceable to the International System of Units. To meet the quality assurance needs in biomonitoring measurements of perchlorate and the related anions that affect thyroid health, the National Institute of Standards and Technology (NIST), in collaboration with the Centers for Disease Control and Prevention (CDC), developed Standard Reference Material (SRM) 3668 Mercury, Perchlorate, and Iodide in Frozen Human Urine. SRM 3668 consists of perchlorate, nitrate, thiocyanate, iodine, and mercury in urine at two levels that represent the 50th and 95th percentiles, respectively, of the concentrations (with some adjustments) in the US population. It is the first CRM being certified for perchlorate. Measurements leading to the certification of perchlorate were made collaboratively at NIST and CDC using three methods based on liquid or ion chromatography tandem mass spectrometry. Potential sources of bias were analyzed, and results were compared for the three methods. Perchlorate in SRM 3668 Level I urine was certified to be 2.70?±?0.21?μg?L(-1), and for SRM 3668 Level II urine, the certified value is 13.47?±?0.96?μg?L(-1).     

A silver electrode in the potentiometric titration of thiols

A silver wire immersed in a thiol solution gives a potential responsive to the thiol concentration, and is a sensitive indicator electrode in the potentiometric titration of thiols with mercury(II) chloride, p-chloromercuryphenyl sulphonate, and silver nitrate at pH 4.5-9.5, 7-9.5 and 9.5 respectively. Titrations of simple thiols such as cysteine or a protein such as albumin are equally successful, but the potential break was smaller for the protein. The end-point could be determined within an increment of titrant equal to 5 nmole of thiol. An inert atmosphere is needed for titration at pH 7.